Chrome containing monoazo dyestuffs



United States Patent 9 CHROME CONTAINING MONOAZO DYESTUFFS Kurt Breig, Koln, and Eugen Glietenberg and Ludwig Niissler, Leverkusen, Germany, assignors to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany No Drawing. Application April 14, 1954, Serial'No. 423,248,

Claims priority, application Germany April 25, 1953 6 Claims. .(Cl. 2,6,0e-147) The present invention relates to new chrome containing monoazo dyestuffs and to a process of making the same; more particularly it relates to chrome complex compounds of monoazo dyestuffs being free from sulfonic acid groups and corresponding to the general formula 2,816,101 Patented Dec. 10, 1957 ICC The following examples illustrate the invention without, however, limiting it thereto:

Example 1' 11.2 grams of 1famine-2-hydroxybenzene-5-sulfomethylarnino-ethane, sulf amide are dissolved in 150 cc. of Water and 10 cc. of hydrochloric acid and diazotized with a 10 percent sodium nitrite solution at 0-5 C. After a short time the diazonium compound precipitates as a crystalline yellow deposit. The acid suspension of it is rendered Weakly acid by adding sodium bicarbonate and then slowly poured into a solution of 8 grams of l-acetylamino-7-hydroxynaphthalene, 1.6 grams of solid sodium hydroxide, 4 grams of sodium carbonate and 150 cc. of water, cooled with ice. After stirring for one hour coupling is finished; the dark blue dyestufi solution shows a p I-l-value of 9.4. After stirring over night at room temfrom sulfonic acid groups can be obtained by coupling diazotized 1-amino-2-hydroxybenzene-sulfamides of the formula thalene, B-hydroxydiphenylene oxide, Z-hydroxycarbazole.

The 1 amino- 2 hydroxybenzene sulfoalkylaminoethane-sulfamides used as diazo components are obtainable by condensing 1-chloro-2-nitrobenzene sulfochlorides with an alkyl taurine, converting the condensation products into the sulfochloride and then into the sulfamide, and finally saponifying the chlorine and reducing the nitro group to the amino group.

perature the solution is adjusted to pH 8 by adding some diluted hydrochloric acid, whereby the dyestulf' precipit-ates. The dyestufii paste obtained after filtering is heated with cc. of water and 10 cc. of caustic soda solution (36 B6.) to 75-:80 0, whereby the dyestuif dissolves. At this temperature cc. of a chromingsolution containing 42.6 grams of potassium bichromate and 78 grams of glucose per litre is run in. Thereafter the solution is stirred for 20 minutes at 80 C. After cooling the dyestuff solution to 40 C. it is adjusted to pH 8.5 by adding some diluted hydrochloric acid, whereby the chromed dyestuif precipitates. The black powder thus obtained is the chrome complex of the monoazo dyestuflE of the formula which dissolves well, in hot. water and dyes wool from neutral as, well asweakly acid bath black-blue shades of good fElSt-HQSS; to washing and very good fastness to light.

Example 2 run into a solution of 6.95 grams of 1-phenyl-3-methyl-5- pyrazolone, 1.6 grams of solid sodium hydroxide, 4 grams of sodium carbonate and 200 cc. oi water, cooled with ice. The coupling mixture is stirred over night at pH 8. The; dyestuif precipitates without addition of. sodium 1 chloride; after filtering cc. of a solution of ammonium chrome-salicylate (corresponding to 1.52v grams of cr Q is added, and the mixture is heated to the boil for 2 our T h ot solu ion 1.2 p r nt i odiu h oride are. added. on ooli ghe. hrom ddycstuttercc pi- 3 tates. It is the chrome complex of the monoazo dyestufi of the formula HO-C S O LIN-C Hz. CHg-S :.NH1

and dyes wool from neutral as well as weakly acid bath reddish orange shades of very good fastness to light as well as of good levelling power and good fastness to washing.

Example 3 11.2 grams of 1-amino-Z-hydroxybenzene-S-sulfomethylamino-ethane sulfamide are diazotized as described in Example 1 and coupled with a solution of 7.3 grams of 3-hydroxy-diphenyleneoxide, 1.6 grams of solid sodium hydroxide and 4 grams of sodium carbonate in 200 cc. of water. After stirring overnight the solution is adjusted to pH 9 by adding some diluted hydrochloric acid, and the precipitated dyestuif is filtered by suction. The chromed dyestuif obtained according to one of the methods described in the foregoing examples represents a dark brown powder which dissolves in hot water with a brown color and dyes wool from neutral or weakly acid bath somewhat violetish brown shades of very good fastness to light and washing. The dyestutf is the chrome complex 1 of the monoazo dyestuff of the formula OH HO Example 4 OH HO CHLCOHN Dyestufis of very similar properties are obtained, if in the above examples in the diazo components used one or both hydrogen atoms of the terminal amide group are replaced by methyl, ethyl or hydroxyethyl i. e. if instead of .1 7 amino 2-hydroxybenzene-S-sulfomethylaminmethane sulfamide the corresponding sulfomethylamide, sulfodimethylamide, sulfoethylamide, sulfodiethylamide,

sulfo-fi-hydroxyethylamide, sulfo-di-fi-hydroxyethylamide, sulfomethyl ethylamide, sulfomethyl-p-hydroxy-ethylamide, sulfoethyl-fl-hydroxyethylamide are used as diazo components.

We claim:

1. Chrome complex compounds of monoazo dyestuffs free from sulfonic acid groups corresponding to the formula wherein A stands for the radical of a coupling component being coupled in o-position to a hydroxy group, R and R stand for members selected from the group consisting of hydrogen, lower alkyl, and lower hydroxy alkyl, and R stands for lower alkyl.

2. Chrome complex compounds of monoazo dyestuffs free from sulfonic acid groups corresponding to the formula wherein A stands for the radical of a coupling component being coupled in o-position to a hydroxy group, R and R stand for members selected from the group consisting of hydrogen, lower alkyl and lower hydroxy alkyl.

3. Chrome complex compounds of monoazo dyestutfs free from sulfonic acid groups corresponding to the formula N=NA R1 s0,.N0H,.0H-s0,.N

wherein A stands'for the radical of a coupling component being coupled in oposition to a hydroxy group, R and R stand for members selected from the group consisting of hydrogen, lower alkyl and lower hydroxy alkyl.

4. Chrome complex compound of the monoazo dyestufi corresponding to the formula OH HO CH:.C O .HN

5. Chrome complex compound of the monoazo dyestutf corresponding to the formula HO.C N

Q sohlf-cmcnrsomn,

6. Chrome complex compound of the monoazo dyestuff corresponding to the formula CHaCOJIN References Cited in the file of this patent UNITED STATES PATENTS Widmer et a1 Sept. 9, 1952 

1. CHROME COMPLEX COMPOUNDS OF MONOAZO DYESTUFFS FREE FROM SULFONIC ACID GROUPS CORRESPONDING TO THE FORMULA 